The First Crystal Structure of a Germanium(II) Amide with a Germanium - Lithium Bond and Its Behavior Towards Oxygen and Water

Abstract

The Ge-Li bond in 1 reacts readily with water and oxygen to give 2 (Li/H exchange) and 3 (insertion), respectively. In both cases the partial charge and the oxidation state of the germanium atom changes. All compounds were characterized by X-ray crystallography.

Synthesis and Reactivity of Acyclic Germanimines: Silyl Rearrangement and Cycloadditions

“…The 1 H NMR spectrum reveals only one environment for the SiMe 3 protons; however, resonances corresponding to the newly formed terminal alkene are observed at δ 5.27 and 5.16 ppm. The GeH resonance is observed at δ 6.47 ppm, downfield to that reported in Veith’s triamido germanium hydride complex, [( t Bu­{OSiMe 2 NHPh} 3 )­GeH] . The X-ray diffraction study of 5 (Figure ) confirmed the connectivity, with the propylene group containing CC bond lengths (1.324(3) and 1.501(3) Å for C(19)C(20) and C(19)C(21), respectively) consistent with double and single bonds in contrast to the single CC bond lengths found in the aliphatic isopropyl group (1.531(3) and 1.536(3) Å for C(22)C(23) and C(22)C(21), respectively).…”

“…The GeH resonance is observed at δ 6.47 ppm, downfield to that reported in Veith's triamido germanium hydride complex, [(tBu{OSiMe 2 NHPh} 3 )GeH]. 34 The X-ray diffraction study of 5 (Figure 2) confirmed the connectivity, with the propylene group containing CC bond lengths (1.324(3) Reactivity Studies. Our reactivity studies were directed at the GeN bond of germanimine 3 due its relative stability compared to both germanimines 2 and 4.…”

Synthesis and Complexation of a Free Germanide Bearing a Tridentate N-Heterocyclic Substituent

“…The substituent (tmim)­H 3 was synthesized and deprotonated according to published procedures. , Subsequently, the germanide 1 was synthesized by nucleophilic substitution of chloride for the tmim 3– trianion on GeCl 2 ·dioxane (Scheme ), which is a common approach to synthesize germanides. − ,, The germanide was obtained either as its sodium salt 1 -Na or as its potassium salt 1 -K. The synthesis of 1 -Na requires an excess of GeCl 2 ·dioxane to reach completion, which is tentatively attributed to formation of insoluble NaGeCl 3 . In contrast, a stoichiometric amount of GeCl 2 ·dioxane was sufficient for the synthesis of 1 -K. Therefore, the potassium salt 1 -K was used for complexation studies.…”

“…All-nitrogen substituted germanides similar to 1 have received some attention, examples including triazidogermanide A , bicyclo triamido­germanide B , and the zwitterionic tripyrazolyl germanide C (Chart ). − Their coordination chemistry is scarce, and structurally characterized complexes are limited to a tungsten­(II) complex derived from structure A , a gold­(I) complex derived from structure B , and iron­(II) complexes of a tetradentate triphosphinogermyl ligand. − In the current work, the synthesis of compound 1 and its complexation to soft Lewis-acidic metal fragments (CuCl, Cu­(NCMe) 3 , and Fe­(CO) 4 ) is reported. In contrast to the silanide, coordination to the harder Lewis acid FeCl 2 results in at most a weak interaction with a small association constant in solution.…”